Process for the constrained sintering of asymmetrically configured dielectric layers

ABSTRACT

A method to produce a distortion-free asymmetrical low-temperature co-fired ceramic structure comprising at least one layer of glass-containing internal constraining tape and at least one layer of glass-containing primary tape wherein the internal constraining tape and the primary tape are laminated to form an asymmetrical laminate and wherein a release layer is deposited on at least one surface of the laminate forming an assembly, wherein the surface is opposite the position of greatest asymmetry of the laminated layers and wherein the assembly is thermally processed producing a structure exhibiting an interactive suppression of x,y shrinkage.

FIELD OF THE INVENTION

This invention relates to a process which produces flat,distortion-free, zero-shrink, low-temperature co-fired ceramic (LTCC)bodies, composites, modules or packages from precursor green (unfired)laminates of different dielectric tape chemistries that are configuredin an asymmetrical arrangement in the z-axis of the laminate.

BACKGROUND OF THE INVENTION

An interconnect circuit board or package is the physical realization ofelectronic circuits or subsystems from a number of extremely smallcircuit elements electrically and mechanically interconnected. It isfrequently desirable to combine these diverse type electronic componentsin an arrangement so that they can be physically isolated and mountedadjacent to one another in a single compact package and electricallyconnected to each other and/or to common connections extending from thepackage.

Complex electronic circuits generally require that the circuit beconstructed of several levels of conductors separated by correspondinginsulating dielectric tape layers. The conductor layers areinterconnected through the dielectric layers that separate them byelectrically conductive pathways, called via fills.

The use of a ceramic-based green tape to make low temperature co-firedceramic (LTCC) multilayer circuits was disclosed in U.S. Pat. No.4,654,095 to Steinberg. The co-fired, free sintering process offeredmany advantages over previous technologies. However, when largercircuits were needed, the firing shrinkage proved too broad to meet theneeds. Given the reduced sizes of the current generation of surfacemount components, the shrinkage tolerance (reproducibility of shrinkage)has proved too great to permit the useful manufacture of LTCC laminatesmuch larger than 6″ by 6″. This upper limit continues to be challengedtoday by the need for greater circuit density as each generation of newcircuits and packages evolves. In turn this translates into ever-smallercomponent sizes and thereby into smaller geometry's including narrowerconductor lines and spaces and smaller vias on finer pitches in thetape. All of this requires a much lower shrinkage tolerance than couldbe provided practically by the free sintering of LTCC laminates.

A method for reducing X-Y shrinkage during firing of green ceramicbodies in which a release layer, which becomes porous during firing, isplaced upon the ceramic body and the assemblage is fired whilemaintaining pressure on the assemblage normal to the body surface wasdisclosed in U.S. Pat. No. 5,085,720 to Mikeska. This method used tomake LTCC multilayer circuits provided a significant advantage overSteinberg, as a reduction X-Y shrinkage was obtained through thepressure assisted method.

An improved co-fired LTCC process was developed and is disclosed in U.S.Pat. No. 5,254,191 to Mikeska. This process, referred to as PLAS, anacronym for pressure-less assisted sintering, placed a ceramic-basedrelease tape layer on the two major external surfaces of a green LTCClaminate. The release tape controls shrinkage during the firing process.Since it allows the fired dimension of circuit features to be morepredictable, the process represents a great improvement in the firedshrinkage tolerance. During the release tape-based constrained sinteringprocess, the release tape acts to pin and restrain any possibleshrinkage in x- and y-directions. The release tape itself does notsinter to any appreciable degree and is removed prior to any subsequentcircuit manufacturing operation.

In a more recent invention, U.S. Patent Application 60/385,697, theteachings of constrained sintering are extended to include the use of anon-fugitive, non-removable, non-sacrificial or non-release, internalself-constraining tape. The fired laminate comprises layers of a primarydielectric tape which define the bulk properties of the final ceramicbody and one or more layers of a secondary or self-constraining tape.The sole purpose of the latter is to constrain the sintering of theprimary tape so that the net shrinkage in the x, y direction is zero.This process is referred to as a self-constraining process and theacronym SCPLAS is applied. The shrinkage tolerances achieved by thisprocess are very similar to those achieved by the release-tape basedconstrained sintering process. The self-constraining tape is placed instrategic locations within the structure and remains part of thestructure after co-firing is completed. There is no restriction on theplacement of the self-constraining tape other than that z-axis symmetryis preserved.

Therefore, symmetrical-only arrangements were available to the circuitdesigner which has proved to be a significant limitation to thecapabilities of LTCC technology. It restricts the designer's freedom toprovide the optimal circuit configuration both from the viewpoint ofperformance, cost and form factor. The current invention with itsasymmetical arrangement removes this limitation. It allows the circuitdesigner a greater flexibility to use the optimal number of tape layers,the most compatible companion conductor, resistor and dielectricmaterials in achieving the highest-quality circuit function.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is an illustration of asymmetrical structures of the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

The current invention extends the teachings of constrained sintering tothe production of large area camber-free, co-fired LTCC structures thatare derived from asymmetric arrangements of low dielectric constanttape, and high k dielectric constant tape materials, each of a differentchemistry. It combines the use both of internal, permanent,self-constraining tape and external, removable release constrainingtape.

Asymmetric structures cannot be co-fired flat by conventional processingtechniques. They tend to bow or camber in a concave manner, i.e., thetwo edges of the laminate will be significantly higher than thecenter-point in the direction perpendicular to the plane of maximumasymmetry.

In a preferred embodiment of this invention, as shown in FIG. 1, aninternal constraining layer (102) is formulated to provide aself-constraining function and an embedded capacitor function within aLTCC assembly.

The properties of the processed internal constraining layer provide arigid physical form restraining x and y shrinkage of primary tapes (101)and impart functional properties to the final LTCC assembly. Theinternal constraining tape precedes the sintering of the primary tapelayers. To prevent bowing and permanent structural distortion afterco-firing because of the difference in dielectric chemistries withoutthe need to symmetrically balance it with dummy or compensating layers,a layer of removable, non permanent release layer (201) is applied tothe outside surface directly opposite the source of greatest asymmetry.This enables extremely asymmetric structures to be fired flat. Afterfiring, the release layer is removed using conventional brushing or sandblasting methods.

A conventional LTCC primary tape (101) typically processes attemperatures near 850° C. When a conventional release layer (201) isused, it must not sinter or become part of the final LTCC body tofunction properly. Contrary to that, an internal constraining tape (102)as utilized in the present invention contains glasses that flow,densify, and become rigid at temperatures significantly below 850° C.,which is a standard process temperature.

The internal constraining tape becomes part of the final LTCC body. Thissignificantly increases the performance requirements for the internalconstraining tape material. The electrical properties (i.e., dielectricconstant) of the internal constraining tape may also be adjusted with achoice of materials that make up the tape. This makes possible the useof more than one chemical type of primary tape to locally control thedielectric and other electrical properties of a portion of a LTCCcircuit.

The primary tape (101) is generally the majority tape in a LTCC assemblyand the resultant fired assembly derives its mechanical and electricalcharacteristics from it. In most situations the internal constrainingtape has a minority presence in the structure. It can be usedeffectively to locally modify aspects of the dielectric and otherelectrical performance of the assembly, but its biggest influence is tocontrol the physical structure by constraining its x,y shrinkagesubstantially to zero.

During the heating of the assembly of the present invention, the glassin the internal constraining tape (high k, with a typical range of10-5000) attains its transition temperature (the temperature at whichthe glass softens and flows) earlier than the glass of the primary tape(low k, with a typical range of 6 to 10) and it flows sufficiently tocoat the surface particles of the adjacent layers of the primary tape.Since the crystallization temperature of the internal constraining tapeglass is close to its transition temperature, crystallization occursvery soon after. This has the result of stiffening the glass andsignificantly raising its composite viscosity or elevating itsre-melting temperature beyond the peak firing temperature of 825 to 875°C. of the first co-firing and/or subsequent post-firing process.

Although crystallization is a preferred method to rigidify tape afterthe densification and flow period of a glass filled tape, phaseimmiscibility using glass or glass-filler mixtures to effectivelyrigidify the tape is also a possible method. This process from sinteringonset to rigidification can be measured for glass and fillercombinations by the use of TMA, Thermo-mechanical analysis. For example,preferably the glass in the primary tape exhibits an onset ofdimensional change as measured in TMA of about 700° C. or higher.Preferably the glass in the constraining tape exhibits an onset ofdimensional change as measured in TMA of about 75° C. or more preferably100 to 150° C. lower than the primary tape.

The constraining influence of the primary tape ensures that x,yshrinkage in the internal constraining tape is very small, if not zero.Subsequent increases in temperature cause the internal constraining tapeto sinter fully and its glass to complete its crystallization. Since asuitable glass will, typically, develop in excess of 50 volume %crystalline phases, the internal constraining tape body becomes rigidwhen dominated by the volumetric accumulation of crystalline content offiller and in situ formation of crystal from the glass. Then, when thetransition temperature of the primary tape glass is achieved and flowoccurs, it is kept physically in place by its previous interaction withthe internal constraining tape. Thus, the already-sintered internalconstraining tape layers become the constraining force and the primarytape is constrained while sintering to shrink only in the z-direction.Once the assembly is fully sintered and has cooled down, the assemblywill be seen to possess the same dimensions in the x,y direction as theoriginal “green” or unfired assembly. The layers of the now chemicallyreacted inorganic components of the two or more individual tapes used inthe assembly are interleaved in various configurations. The only stillobservable boundaries being those where tapes of different chemistrieswere placed adjacent to each other.

Such an innovation offers the advantages of facilitating cofireableconductors on the surface opposite the side with the release tape andalso relieves the practical restrictions that externally-constrainedsintered structures experience as the layer count is increased and theconstraining influence of the external release tape is felt less andless. In addition, the use of the internal constraining tape allows theformation of exactly dimensioned, non-shrink cavities in a tapestructure. Both blind and through cavities can be produced by thisconstrained sintering technique.

In order to meet the performance requirements of LTCC circuitmanufacturers, additional material performance factors must beconsidered beyond the simple process of constraining the x,y shrinkagein the green tape assembly when thermally processed. The coefficient ofthermal expansion of both the internal constraining tape and the primarytape must be sufficiently close in magnitude to provide for theproduction of 6″×6″ or larger ceramic boards consisting of many layersof laminated green tape materials. Inattention to this could result instress induced cracking in the fired ceramic LTCC body during thetemperature descending portion of the furnace firing or thereafter.

Another design factor is created because the internal constraining tapemust be thermally processed to a rigid body prior to the primary tape toprovide proper system x,y constraint. This means that the glass-fillermaterial in the internal constraining tape should be designed to attaina lower composite viscosity to the primary tape, but at approximately50-150° C. lower in temperature and preferably in the range of 80-150°C. It should be noted that the above assessment was based on a beltfurnace firing profile at an ascending rate of 6-8° C. per minutebetween 450° C. and 800° C. Such a profile is commonly used to achievehigh throughput in mass production of LTCC circuit substrates. However,a smaller temperature difference (e.g. <50° C.) can also be effective ifthe firing profile in a multiple zone belt or box furnace provides aplateau to facilitate the full densification, and/or crystallization,and rigidification of the internal constraining tape. It should alsoprovide sufficient compatibility between internal constraining andprimary tapes during the densification to maintain the strength andbonding at the respective tape interfaces. This compatibility can beinfluenced by tape formulation, physical characteristics of theconstituents and changes in thermal processing conditions. Theelectrical properties of the internal constraining tape material mustalso meet performance requirements for high frequency circuitapplications.

The release layer for use in the method of the invention is comprised ofnon-metallic particles dispersed in a solid organic polymer binder. Asmentioned above, it is preferred that the non-metallic particles in therelease layer have a lower sintering rate than the inorganic binder ofthe primary tape layer being fired at conventional temperatures with apreferred being 850° C. and that the wetting angle of the inorganicbinder on the primary tape layer and the viscosity of the inorganicbinder be such that glass penetration into the release layer is duringsubsequent firing is no more than 50 μm. Thus, the composition of theinorganic solids component of the release layer is likewise not criticalas long as it does not undergo sintering during firing and as long asthe wetting angle and the viscosity of the inorganic binder in theprimary tape layer being fired are within the preferred bounds whichprohibit substantial penetration into the release layer. Although theinorganic non-metallic solids used in the release layer may be the sameas those used in the primary tape, mullite, quartz, Al₂O₃, CeO₂, SnO₂,MgO, ZrO₂, BN and mixtures thereof are preferred. Furthermore, glassymaterials can be used provided their softening points are sufficientlyhigh so that they do not undergo sintering when they are fired inaccordance with the invention.

The release layer can be applied in the form of a flexible tape, a thickfilm paste, spray, dip, roll, etc. Regardless of the form in which thelayer is applied, it is essential that the layer be flexible in order toattain close conformance to the surface of the LTCC assembly to reduceand preferably minimize the size of any gaps (flaws) at the releaselayer/primary tape interface and increase the critical stress value atthe interface. In general, the same binder polymers which are suitablefor the unfired internal constraining and primary tape layers will besuitable for the release layer when it is applied as a tape.

As used herein, the terms “thick film” and “thick film paste” refer todispersions of finely divided solids in an organic medium, which are ofpaste consistency and have a rheology suitable for screen printing andspray, dip or roll-coating. The organic media for such pastes areordinarily comprised of liquid binder polymer and various rheologicalagents dissolved in a solvent, all of which are completely pyrolyzableduring the firing process. Such pastes can be either resistive orconductive and, in some instances, may even be dielectric in nature.Such compositions may or may not contain an inorganic binder, dependingupon whether or not the functional solids are required to be sinteredduring firing. Conventional organic media of the type used in thick filmpastes are also suitable for the internal constraining layer. A moredetailed discussion of suitable organic media materials can be found inU.S. Pat. No. 4,536,535 to Usala.

To ensure the formation of interconnected porosity in the release layerin order to provide an escape pathway for polymer decompositionproducts, the pore escape channels (void or pore structure) between theindividual particles within the release layer must be sufficient in sizeand remain open during heatup. For the pore channels to remain openduring heatup, the sintering rate of the release layer material must beless than the sintering rate of the primary tape layer being fired aspreviously discussed. The pore structure in the release layer isdetermined by the characteristic particle arrangement or assembly withinthe layer. The arrangement or packing of particles in the layer isinfluenced by several factors including: the volume fraction of solids,the solids particle size, size distribution, and shape, the degree ofdispersion of the particles in the initial casting, the dryingcharacteristics of the casting, whether the layer is applied by dip orspray slurrying, and how the layer is applied. Furthermore, the pore orvoid structure in a tape, spray, or dip layer that contains a polymermatrix will most likely be different in the layer after the polymer ispyrolyzed. Keeping the foregoing conditions in mind, it is possible topack particles to a bulk density of ˜90 vol % solids. On the other hand,a lower limit on bulk density of ˜10 vol % solids should be practicableto provide sufficiently large pore channels without serious degradationof the x,y compressive stress capability of the layer and withoutsignificant penetration of the glass into the layer. A more detaileddiscussion of a suitable release layer can be found in U.S. Pat. No.5,254,191, which is incorporated herein by reference.

Internal constraining and primary tape components and formulationsfollow. The internal constraining tape (102) is further characterized ascomposed of a filler ceramic material such as Al₂O₃, ZrO₂, ZrSiO₄, etc.,with a crystallizable or filler reactable glass composition so that itsflow, densification and rigidification during firing proceed theremaining layers of primary tape. Although a constraining or primarytape normally may consist of a glass and filler, it may be designed byskilled artisans to utilize more than one glass or more than one filler.The physical act of restricting the x,y shrinkage of the internalconstraining tape by the primary tape during thermal processing is quitesimilar to the externally applied release layers of a conventionalprimary tape assembly. It is to be noted, however, that although theterms of “primary tape” and “internal constraining tape” are used inthis invention, the “primary tape” constrains the “internal constrainingtape” during its lower temperature sintering/crystallization process;whereas the already sintered “internal constraining tape” constrains the“primary tape” during its higher temperature firing. The requirementsfor suitable materials to serve as a non-sacrificed internalconstraining tape are however different. The material requirements areconsidered below.

Specific examples of glasses that may be used in the primary or internalconstraining tape are listed in Table 1. Preferred glass compositionsfound in the internal constraining tape comprise the following oxideconstituents in the compositional range of: B₂O₃ 6-13, BaO 20-22, Li₂O0.5-1.5, P₂O₅ 3.5-4.5, TiO₂ 25-33, Cs₂O 1-6.5, Nd₂O₃ 29-32 in weight %.The more preferred composition of glass being: B₂O₃ 11.84, BaO21.12,Li₂O 1.31, P₂O₅ 4.14, TiO₂ 25.44, Cs₂O 6.16, Nd₂O₃ 29.99 in weight%. Another preferred glass comprises the following oxide constituents inthe compositional range of: SiO₂ 12-14, ZrO₂ 3-6, B₂O₃ 20-27, BaO 12-15,MgO 33-36, Li₂O 1-3, P₂O₅ 3-8, Cs₂O 0-2 in weight %. The preferredcomposition of glass being: SiO₂ 13.77, ZrO₂ 4.70, B₂O₃ 26.10, BaO14.05, MgO 35.09, Li₂O 1.95, P₂O₅ 4.34 in weight %.

Preferred glasses for use in the primary tape comprise the followingoxide constituents in the compositional range of: SiO₂ 52-54, Al₂O₃12.5-14.5, B₂O₃ 8-9, CaO 16-18, MgO 0.5-5, Na₂O 1.7-2.5, Li₂O 0.2-0.3,SrO 0-4, K₂O 1-2 in weight %. The more preferred composition of glassbeing: SiO₂ 53.50, Al₂O₃ 13.00, B₂O₃ 8.50, CaO 17.0, MgO 1.00 Na₂O 2.25,Li₂O 0.25, SrO 3.00, K₂O 1.50 in weight %.

In the primary or constraining tape the D₅₀ (median particle size) offrit is preferably in the range of, but not limited to, 0.1 to 5.0 milsand more preferably 0.3 to 3.0 mils.

The glasses described herein are produced by conventional glass makingtechniques. The glasses were prepared in 500-1000 gram quantities.Typically, the ingredients are weighed then mixed in the desiredproportions and heated in a bottom-loading furnace to form a melt inplatinum alloy crucibles. As well known in the art, heating is conductedto a peak temperature (1450-1600° C.) and for a time such that the meltbecomes entirely liquid and homogeneous. The glass melts were thenquenched by counter rotating stainless steel roller to form a 10-20 milthick platelet of glass. The resulting glass platelet was then milled toform a powder with its 50% volume distribution set between 1-5 microns.The glass powders were then formulated with filler and organic medium tocast tapes as detailed in the Examples section. The glass compositionsshown in Table 1 represent a broad variety of glass chemistry (highamounts of glass former to low amounts of glass former). The glassformer oxides are typically small size ions with high chemicalcoordination numbers such as SiO₂, B₂O₃, and P₂O₅. The remaining oxidesrepresented in the table are considered glass modifiers andintermediates.

TABLE 1 (wt. %) Glass # SiO₂ Al₂O₃ PbO ZrO₂ B₂O₃ CaO BaO MgO Na₂O Li₂OP₂O₅ TiO₂ K₂O Cs₂O Nd₂O₃ SrO 1 6.08 23.12 4.50 34.25 32.05 2 13.77 4.7026.10 14.05 35.09 1.95 4.34 3 55.00 14.00 9.00 17.50 4.50 4 11.91 21.240.97 4.16 26.95 4.59 30.16 5 56.50 9.10 17.20 4.50 8.00 0.60 2.40 1.70 611.84 21.12 1.31 4.14 25.44 6.16 29.99 7 52.00 14.00 8.50 17.50 4.752.00 0.25 1.00 8 6.27 22.79 0.93 4.64 33.76 31.60 9 9.55 21.73 0.92 4.2332.20 1.24 30.13 10 10.19 21.19 0.97 4.15 28.83 4.58 30.08 11 13.67 5.0325.92 13.95 34.85 1.94 4.64 12 12.83 4.65 21.72 13.09 34.09 1.96 11.6513 13.80 4.99 25.86 13.45 33.60 2.09 4.35 1.87 14 52.00 14.00 9.00 17.505.00 1.75 0.25 0.50 15 53.5 13.00 8.50 17.00 1.00 2.25 0.25 1.50 3.00 1613.77 4.70 22.60 14.05 35.09 1.95 7.84 17 54.00 12.86 8.41 16.82 0.992.23 0.25 1.48 2.96

Ceramic filler such as Al₂O₃, ZrO₂, TiO₂, BaTiO₃ or mixtures thereof maybe added to the castable composition used to form the tapes in an amountof 0-50 wt. % based on solids. Depending on the type of filler,different crystalline phases are expected to form after firing. Thefiller can control dielectric constant and loss over the frequencyrange. For example, the addition of BaTiO₃ can increase the dielectricconstant significantly.

Al₂O₃ is the preferred ceramic filler since it reacts with the glass toform an Al-containing crystalline phase. Al₂O₃ is very effective inproviding high mechanical strength and inertness against detrimentalchemical reactions. Another function of the ceramic filler isrheological control of the entire system during firing. The ceramicparticles limit flow of the glass by acting as a physical barrier. Theyalso inhibit sintering of the glass and thus facilitate better burnoutof the organics. Other fillers, α-quartz, CaZrO₃, mullite, cordierite,forsterite, zircon, zirconia, BaTiO₃, CaTiO₃, MgTiO₃, SiO₂, amorphoussilica or mixtures thereof may be used to modify tape performance andcharacteristics. It is preferred that the filler has at least a bimodalparticle size distribution with D50 of the larger size filler in therange of. 1.5 and 2 microns and the D50 of the smaller size filler inthe range of 0.3 and 0.8 microns.

In the formulation of internal constraining and primary tapecompositions, the amount of glass relative to the amount of ceramicmaterial is important. A filler range of 20-40% by weight is considereddesirable in that the sufficient densification is achieved. If thefiller concentration exceeds 50% by wt., the fired structure is notsufficiently densified and is too porous. Within the desirableglass/filler ratio, it will be apparent that, during firing, the liquidglass phase will become saturated with filler material.

For the purpose of obtaining higher densification of the compositionupon firing, it is important that the inorganic solids have smallparticle sizes. In particular, substantially all of the particles shouldnot exceed 15 μm and preferably not exceed 10 μm. Subject to thesemaximum size limitations, it is preferred that at least 50% of theparticles, both glass and ceramic filler, be greater than 1 μm and lessthan 6 μm.

The organic medium in which the glass and ceramic inorganic solids aredispersed is comprised of a polymeric binder which is dissolved in avolatile organic solvent and, optionally, other dissolved materials suchas plasticizers, release agents, dispersing agents, stripping agents,antifoaming agents, stabilizing agents and wetting agents.

To obtain better binding efficiency, it is preferred to use at least 5%wt. polymer binder for 90% wt. solids, which includes glass and ceramicfiller, based on total composition. However, it is more preferred to useno more than 30% wt. polymer binder and other low volatility modifierssuch as plasticizer and a minimum of 70% inorganic solids. Within theselimits, it is desirable to use the least possible amount of binder andother low volatility organic modifiers, in order to reduce the amount oforganics which must be removed by pyrolysis, and to obtain betterparticle packing which facilitates full densification upon firing.

In the past, various polymeric materials have been employed as thebinder for green tapes, e.g., poly(vinyl butyral), poly(vinyl acetate),poly(vinyl alcohol), cellulosic polymers such as methyl cellulose, ethylcellulose, hydroxyethyl cellulose, methylhydroxyethyl cellulose, atacticpolypropylene, polyethylene, silicon polymers such as poly(methylsiloxane), poly(methylphenyl siloxane), polystyrene, butadiene/styrenecopolymer, polystyrene, poly(vinyl pyrollidone), polyamides, highmolecular weight polyethers, copolymers of ethylene oxide and propyleneoxide, polyacrylamides, and various acrylic polymers such as sodiumpolyacrylate, poly(lower alkyl acrylates), poly(lower alkylmethacrylates) and various copolymers and multipolymers of lower alkylacrylates and methacrylates. Copolymers of ethyl methacrylate and methylacrylate and terpolymers of ethyl acrylate, methyl methacrylate andmethacrylic acid have been previously used as binders for slip castingmaterials.

U.S. Pat. No. 4,536,535 to Usala, issued Aug. 20, 1985, has disclosed anorganic binder which is a mixture of compatible multipolymers of 0-100%wt. C₁₋₈ alkyl methacrylate, 100-0% wt. C₁₋₈ alkyl acrylate and 0-5% wt.ethylenically unsaturated carboxylic acid of amine. Because the abovepolymers can be used in minimum quantity with a maximum quantity ofdielectric solids, they are preferably selected to produce thedielectric compositions of this invention. For this reason, thedisclosure of the above-referred Usala application is incorporated byreference herein.

Frequently, the polymeric binder will also contain a small amount,relative to the binder polymer, of a plasticizer that serves to lowerthe glass transition temperature (Tg) of the binder polymer. The choiceof plasticizers, of course, is determined primarily by the polymer thatneeds to be modified. Among the plasticizers which have been used invarious binder systems are diethyl phthalate, dibutyl phthalate, dioctylphthalate, butyl benzyl phthalate, alkyl phosphates, polyalkyleneglycols, glycerol, poly(ethylene oxides), hydroxyethylated alkyl phenol,dialkyldithiophosphonate and poly(isobutylene). Of these, butyl benzylphthalate is most frequently used in acrylic polymer systems because itcan be used effectively in relatively small concentrations.

The solvent component of the casting solution is chosen so as to obtaincomplete dissolution of the polymer and sufficiently high volatility toenable the solvent to be evaporated from the dispersion by theapplication of relatively low levels of heat at atmospheric pressure. Inaddition, the solvent must boil well below the boiling point or thedecomposition temperature of any other additives contained in theorganic medium. Thus, solvents having atmospheric boiling points below150° C. are used most frequently. Such solvents include acetone, xylene,methanol, ethanol, isopropanol, methyl ethyl ketone, ethyl acetate,1,1,1-trichloroethane, tetrachloroethylene, amyl acetate, 2,2,4-triethylpentanediol-1,3-monoisobutyrate, toluene, methylene chloride andfluorocarbons. Individual solvents mentioned above may not completelydissolve the binder polymers. Yet, when blended with other solvent(s),they function satisfactorily. This is well within the skill of those inthe art. A particularly preferred solvent is ethyl acetate since itavoids the use of environmentally hazardous chlorocarbons.

In addition to the solvent and polymer, a plasticizer is used to preventtape cracking and provide wider latitude of as-coated tape handlingability such as blanking, printing, and lamination. A preferredplasticizer is BENZOFLEX® 400 manufactured by Rohm and Haas Co., whichis a polypropylene glycol dibenzoate.

EXAMPLES

Quantitative examples of the present invention are provided in Table 2.The thickness values depicted in the columns of Table 2 representspecified dimensions of the tapes found in the LTCC laminate. Thedimensions found in the Table in no way limit the invention, but arerepresented embodiments for demonstration purposes. Note the dimensionsin the Table are “green” measurements meaning unfired.

The examples were prepared according to the configuration (as definedabove) of the various laminates (see dimensions A, B, C and D in Table2). Three types of green tape used in this invention include the primarytape (101) (thickness not exceeding 20 mils and preferably 1 to 10mils), the internal constraining tape (102) (thickness not exceeding 10mils and preferably 1 to 3 mils), and the release tape (201) (thicknessnot exceeding 10 mils and preferably 1 to 5 mils). According to thedefined configuration of the laminate, the selected tapes are blankedwith corner registration holes into sheets of dimensions ranging from3″×3″ to 6″×6″ or larger sizes. These green tape sheets are typicallyused as the dielectric or insulating material for multilayer electroniccircuits. To connect various layers of the multilayer circuit, via holesare formed in the green tape. This is typically done by mechanicalpunching. However, a sharply focused laser can also be used tovolatilize the organic substance and form via holes in the green tape.Typical via hole sizes range from 0.004″ to 0.25″. The interconnectionsbetween layers are formed by filling the via holes with a thick filmconductive composition. This composition is usually applied by screenprinting. Each layer of circuitry is completed by screen printingconductor tracks. Also, resistor compositions or high dielectricconstant compositions can be printed on selected layer(s) to formresistive or capacitive circuit elements. Furthermore, speciallyformulated high dielectric constant green tapes similar to those used inthe multilayer capacitor industry can be incorporated as part of themultilayer circuitry.

After each layer of the circuit is completed, the individual layers arecollated and laminated. A confined uniaxial or isostatic pressing die isused to insure precise alignment between layers. Firing is carried outin a standard thick film conveyor belt furnace or in a box furnace witha programmed heating cycle. This method will, also, allow top or bottomconductors to be co-fired as part of the constrained sintered structurebecause the release tape is used only at the bottom or top layer of theasymmetrical laminate structure. A typical procedure of water washing,mechanical burnishing or sand blasting is used to remove the releasetape and clean the resultant laminate after firing. The parts were thenevaluated for any shrinkage and substrate camber.

As used herein, the term “firing” means heating the assemblage in anoxidizing atmosphere such as air to a temperature, and for a timesufficient to pyrolyze (burn-out) all of the organic material in thelayers of the assemblage to sinter any glass, metal or dielectricmaterial in the layers and thus densify the entire laminate.

It will be recognized by those skilled in the art that in each of thelaminating steps the layers must be accurate in registration so that thevias are properly connected to the appropriate conductive path of theadjacent functional layer.

The term “functional layer” refers to the printed green tape, which hasconductive, resistive or capacitive functionality. Thus, as indicatedabove, a typical green tape layer may have printed thereon one or moreresistor circuits and/or capacitors as well as conductive circuits.

Example 5 in Table 2 describes a symmetrical configuration thatdemonstrates the flatness of structure that can be achieved afterfiring. The measured camber was less than 0.003 inches per one inch ofdiagonal substrate length. Example 6 in Table 2 represents anasymmetrical condition with no release tape present. The severe camberobtained (˜0.010 inches per one inch of diagonal length) demonstratesthe difficulty of successfully co-firing such structures.

All of the conditions using the bold large type produced flat parts witha camber of less than 0.003 inches per one inch of diagonal substratelength. Those in the smaller type produced camber in excess of thislimit. Example 17 represents an asymmetrical configuration in whichrelease tape was applied to both sides of the laminate. This is contraryto the teachings of this patent. The measured camber was greater than0.015 inches per one inch of diagonal substrate length. This exampleserves to demonstrate the significance of the application of releasetape to only one side of the laminate, namely the side that is oppositethe layers of greatest asymmetry.

Tape compositions used in the examples were prepared by ball milling thefine inorganic powders and binders in a volatile solvent or mixturesthereof. To optimize the lamination, the ability to pattern circuits,the tape burnout properties and the fired microstructure development,the following volume % formulation of slip for constraint and primarytape was found to provide advantages. The formulation of typical slipcompositions is also shown in weight percentage, as a practicalreference. The inorganic phase is assumed to have a specific density of4.5 g/cc for glass and 4.0 g/cc for alumina and the organic vehicle isassumed to have a specific density of 1.1 g/cc. The weight % compositionchanges accordingly when using glass and oxides other than alumina asthe specific density maybe different than those assumed in this example.

Typical Primary and Internal Constraining Tape Compositions:

Volume % Weight % Inorganic phase 41.9 73.8 Organic phase 58.1 26.2

The above volume and weight % slip composition may vary 5 dependent onthe desirable quantity of the organic solvent and/or solvent blend toobtain an effective slip milling and coating performance. Morespecifically, the composition for the slip must include sufficientsolvent to lower the viscosity to less than 10,000 centipoise; typicalviscosity ranges are 1,000 to 4,000 centipoise. An example of a slipcomposition is provided in Table 3. Depending on the chosen slipviscosity, higher viscosity slip prolongs the dispersion stability for alonger period of time (normally several weeks). A stable dispersion oftape constituents is usually preserved in the as-coated tape.

TABLE 3 Primary and Internal constraining Tape Slip Compositions:Component Weight % Acrylate and methacrylate polymers 4.6 Phthalate typeplasticizers 1.1 Ethyl acetate/isopropyl alcohol mixed solvent 20.4Glass powder 50.7 Alumina powder 23.2

The glasses used in the Examples were melted in Pt/Rh crucibles at1450-1600° C. for about 1 hour in an electrically heated furnace.Glasses were quenched by metal roller as a preliminary step and thensubjected to particle size reduction by milling. The glass particleswere adjusted to a 5-7 micron mean size by milling prior to formulationas a slip. Since additional milling was utilized in the fabrication ofslip, the final mean size is normally in the range of 1-3 microns.

The release layer was comprised of non-metallic particles dispersed in asolid organic polymer binder. An example of a slip composition for therelease tape is given in Table 4.

TABLE 4 Non-permanent Release Tape Slip Composition Component Weight %Acrylic binder 6.8 Phthalate type plasticizers 2.0 Ethylacetate/isopropanol solvent 28.7 Alumina powder 62.5

Example 1

A laminate was prepared using the following materials:

A low k primary tape, tape 1, as described above in Table 3 and with theglass powder containing 64 volume percent of a glass with thecomposition in weight percent of: SIO₂ 53.5, Al₂O₃ 13.0, B₂O₃ 8.5, CaO17.0, MgO 1.0, Na₂O 2.25, Li₂O₃ 0.25, K₂O 1.50, SrO 3.00 and 36 volumepercent Al₂O₃. The green thickness was 4.5 mils or 114 micrometers.

A high k internal constraining tape, tape 2, as described above in Table3 and with glass powder containing 66.3% volume percent of a glass withthe composition in weight percent of: B₂O₃ 11.84, BaO 21.12, Li₂O 1.31,P₂O₅ 4.14, TiO2 25.44, CsO 6.16, Nd₂O₃ 29.99, and 33.7 volume percent ofAl₂O₃. The green thickness was 2.0 mils or 51 micrometers.

A non-permanent release tape, tape 3, as described in Table 4. The greentape thickness was 5.0 mils or 127 micrometers.

Ten sheets, 6 inches by 6 inches, were cut from a roll of tape 1. Twosheets, 6 inches by 6 inches, were cut from a roll of tape 2. One sheet,6 inches by 6 inches, was cut from a roll of tape 3.

The sheets were then arranged as follows: 2 sheets of tape 1 totaling229 micrometers were placed at the bottom of the stack. On top wasplaced two sheets of tape 2 totaling 102 micrometers. Then 8 sheets oftape 1 totaling thickness of 914 micrometers were placed next insequence. A single sheet of release tape with a thickness of 127micrometers was placed on top of this. The stack was laminated using auniaxial press at 3000 psi at 70° C. for 5 minutes using one orientationand then 5 minutes using an orientation rotated 90°.

After lamination the parts were placed on setters and fired in aconveyer furnace with an air atmosphere where the temperature wasincreased from room temperature to 850° C. and held for 18 minutes andthen allowed to cool back to room temperature the whole process takingapproximately 3 hours and 30 minutes.

The part was then examined for camber by measuring the deflection of itscenter point using a dial gage. Camber is expressed as the deflection ininches of the center point of the substrate divided by the number ofinches along one diagonal (length) of the substrate. The example partdemonstrated less than 0.003 inches per one inch of diagonal substratelength and was judged acceptable. Under normal circumstances partsexhibiting less than 0.003 inches of camber per one inch of diagonalsubstrate length are judged acceptable.

Example 2

Example 1 was repeated using the same type tapes as described in Example1 with sheets cut to 6 inches by 6 inches.

Ten sheets, 6 inches by 6 inches, were cut from a roll of tape 1. Fivesheets, 6 inches by 6 inches, were cut from a roll of tape 2. One sheet,six inches by six inches, was cut from a roll of tape 3.

The sheets were then arranged as follows: 2 sheets of tape 1 to a totalof 229 micrometers were placed at the bottom of the stack. On top ofthis was placed five sheets of tape 2 to a total of 254 micrometers.Then 8 sheets of tape 1 to a total thickness of 914 micrometers wereplaced next in sequence. Finally the single sheet of release tape to athickness of 127 micrometers was placed on top of this. The whole wascollated and then laminated using a uniaxial press at 3000 psi at 70° C.for 5 minutes using one orientation and then an additional 5 minutesusing an orientation rotated 90° from the previous one.

After lamination the parts were placed on setters and fired in aconveyer furnace in an air atmosphere where the temperature wasincreased from room temperature to 850° C. and held for 18 minutes andthen allowed to cool back to room temperature the whole process takingapproximately 3 hours and 30 minutes.

The part was then examined for camber by measuring the deflection of itscenter point using a dial gage. Camber is expressed as the deflection ininches of the center point of the substrate divided by the number ofinches along one diagonal (length) of the substrate. Normally partsexhibiting less than 0.003 inches of camber per inch of diagonalsubstrate length are judged acceptable. The example part demonstratedapproximately 0.005 inches per one inch of diagonal substrate length andwas judged unacceptable.

Example 3

Example 1 was repeated using the same type tapes, but with the differentsized sheets of 3 inches by 3 inches.

Six sheets, 3 inches by 3 inches, were cut from a roll of tape 1. Threesheets, 3 inches by 3 inches, were cut from a roll of tape 2. One sheet,3 inches by 3 inches, was cut from a roll of tape 3.

The sheets were then arranged as follows: 1 sheet of tape 1 to a totalof 114 micrometers was placed at the bottom of the stack. On top of thiswas placed three sheets of tape two to a total of 154 micrometers. Then5 sheets of tape 1 to a total thickness of 572 micrometers were placednext in sequence. Finally the single sheet of release tape to athickness of 127 micrometers was placed on top of this. The whole wascollated and then laminated using a uniaxial press at 3000 psi at 70° C.for 5 minutes using one orientation and then an additional 5 minutesusing an orientation that is rotated 90° from the previous one.

After lamination the parts were placed on setters and fired in aconveyer furnace in an air atmosphere where the temperature wasincreased from room temperature to 850° C. and held for 18 minutes andthen allowed to cool back to room temperature the whole process takingapproximately 3 hours and 30 minutes.

The part was then examined for camber by measuring the deflection of itscenter point using a dial gage. Camber is expressed as the deflection ininches of the center point of a substrate divided by the number ofinches along one diagonal (length) of the substrate. The example partdemonstrated less than 0.003″ per one inch of diagonal substrate lengthand was judged acceptable. Normally parts exhibiting less than 0.003inches of camber per one inch of diagonal substrate length are judgedacceptable.

Example 4

Example 1 was repeated using the same type tapes, but with the differentsized sheets of 3 inches by 3 inches.

Twelve sheets, 3 inches by 3 inches, were cut from a roll of tape 1. Twosheets, 3 inches by 3 inches, were cut from a roll of tape 2. One sheet,six inches by six inches, was cut from a roll of tape 3.

The sheets were then arranged as follows: 2 sheets of tape 1 to a totalof 229 micrometers were placed at the bottom of the stack. On top ofthis was placed two sheets of tape 2 to a total of 102 micrometers. Then10 sheets of tape 1 to a total thickness of 1143 micrometers were placednext in sequence. Finally the single sheet of release tape to athickness of 127 micrometers was placed on top of this. The whole wascollated and then laminated using a uniaxial press at 3000 psi at 70° C.for 5 minutes using one orientation and then an additional 5 minutesusing an orientation rotated 90° from the previous one.

After lamination the parts were placed on setters and fired in aconveyer furnace with an air atmosphere where the temperature wasincreased from room temperature to 850° C. and held for 18 minutes andthen allowed to cool back to room temperature the whole process takingapproximately 3 hours and 30 minutes.

The part was then examined for camber by measuring the deflection of itscenter point using a dial gage. Camber is expressed as the deflection ininches of the center point of the substrate divided by the number ofinches along one diagonal (length) of the substrate. The example partdemonstrated approximately 0.005″ per one inch of diagonal substratelength and was judged unacceptable. Normally parts exhibiting less than0.003″ of camber per one inch of diagonal substrate length are judgedacceptable.

Examples 5 to 17

Examples 5-17 were prepared in a like manner as described in Examples1-4. These examples utilized additional combinations of tapes 1, 2 and 3(in various thicknesses) and the resultant values of camber, acceptableor unacceptable, are summarized in Table 2.

TABLE 2 A B C D (μm) (μm) (μm) (μm) Shrinkage Camber (inch) Totalthickness Total thickness Total thickness Total thickness (%) Deflectionper Laminate of low k tape of high k tape (102) of low k tape (101) ofrelease tape X, Y inch of substrate size (101) on side1 (green) side1to2 (green) on side2 (green) (201) side 2 (green) (fired) diagonallength (fired) Example 1 6″ * 6″ 229 102 914 127 −0.017 <0.003 Example 26″ * 6″ 229 254 914 127 −0.120 ˜0.005 Example 3 3″ * 3″ 114 152 572 127−0.119 <0.003 Example 4 3″ * 3″ 229 102 1143 127 −0.027 ˜0.005 Example 56″ * 6″ 572 102 572  0 −0.050 <0.003 Example 6 3″ * 3″ 114 102 572  0 ND˜0.010 Example 7 3″ * 3″ 0 102 457 127 −0.047 <0.003 Example 8 3″ * 3″114 25 229 127 ND <0.003 Example 9 3″ * 3″ 114 51 343 127 −0.048 <0.003Example 10 3″ * 3″ 229 51 457 127 −0.028 <0.003 Example 11 3″ * 3″ 22951 572 127 −0.015 <0.003 Example 12 3″ * 3″ 229 178 914 127 −0.092<0.003 Example 13 3″ * 3″ 229 102 1715 127 −0.030 ˜0.010 Example 14 3″ *3″ 229 152 914 127 −0.046 ˜0.010 Example 15 3″ * 3″ 229 152 914 254−0.079 <0.003 Example 16 6″ * 6″ 229 254 914 254 −0.151 <0.003 Example17 6″ * 6″ 114 51 457 127 side1 127 ND >0.015 side2

What is claimed is:
 1. A method to produce a distortion-freeasymmetrical low-temperature co-fired ceramic structure comprising atleast one layer of glass-containing internal constraining tape and atleast one layer of glass-containing primary tape wherein the internalconstraining tape and the primary tape are laminated to form anasymmetrical laminate and wherein a release layer is deposited on atleast one surface of the laminate forming an assembly, wherein thesurface is opposite the position of greatest asymmetry of the laminatedlayers and wherein the assembly is thermally processed and the glass ofthe constraining tape initiates sintering before the glass of theprimary tape thus producing a structure exhibiting an interactivesuppression of x,y shrinkage.
 2. The method of claim 1, in which thetape layers are metallized in a planar and in an interconnection manner.3. The method of claim 1 wherein the assembly is populated with surfacemount components.
 4. The method of claim 1 wherein said primary tape hasa dielectric constant in the range of 6 to 10 and said internalconstraining tape has a dielectric constant in the range of 10 to 5000.5. The method of claim 1 wherein the internal constraining tapecomprises filler particles having a bimodal particle size distributionwith D50 of the larger size particles being in the range of 1.5 to 2.0microns and D50 of the smaller size particles being in the range of 0.3to 0.8 microns.
 6. The method of claim 1 wherein the primary tapecomprises filler particles having a bimodal particle size distributionwith D50 of the larger size particles being in the range of 1.5 to 2.0microns and D50 of the smaller size particles being in the range of 0.3to 0.8 microns.
 7. The method of claim 1 wherein the glass of theprimary tape comprises, based on total composition: SiO₂ 52-54, Al₂O₃12.5-14.5, B₂O₃ 8-9, CaO 16-18, MgO 0.5-5, Na₂O 1.7-2.5, Li₂O 0.2-0.3,SrO 0-4, K₂O 1-2 in weight %.
 8. The method of claim 1 wherein the glassof the constraining tape comprises, based on total composition: B₂O₃6-13, BaO 20-22, Li₂O 0.5-1.5, P₂O₅ 3.5-4.5, TiO₂ 25-33, Cs₂O 1-6.5,Nd₂O₃ 29-32 in weight %.
 9. The method of claim 1 wherein the glass ofthe constraining tape comprises, based on total composition: SiO₂ 12-14,ZrO₂ 3-6, B₂O₃ 20-27, BaO 12-15, MgO 33-36, Li₂O 1-3, P₂O₅ 3-8, Cs₂O 0-2weight %.
 10. The method of claim 1 wherein the glass in the primarytape exhibits a dimensional change measured in TMA of about 700° C. orhigher.
 11. The method of claim 1 wherein the glass in the constrainingtape exhibits a dimensional change measured in TMA of at least 75° C.lower than the primary tape.